Methods for treating relaxed hair

ABSTRACT

Methods and kits for treating hair or preventing damage in the relaxing of hair are disclosed herein. Hair that is damaged during a relaxing treatment with hydroxide-containing relaxing agents, can be treated with formulations containing one or more active agents. The active agent formulations can be applied simultaneously with the hair relaxing formulation, or optionally applied immediately following application of the relaxing formulation, to reduce damage and breakage. Use of the active agent formulation along with a relaxing treatment can be used to control the level of curl achieved or retained in the relaxed hair, as compared to the natural amount of curl in the untreated hair.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims benefit of and priority to U.S. ProvisionalApplication No. 62/152,220, filed Apr. 24, 2015, which is incorporatedherein by reference in its entirety.

FIELD OF THE INVENTION

The present invention generally relates to compositions and methods fortreating hair, particularly for repairing disulfide bonds in hairtreated with a lye or alkali-based relaxer and for controlling the levelof curl retention in the relaxed hair.

BACKGROUND OF THE INVENTION

Hair consists of many long, parallel chains of amino acids. Thesechains, or polymers, of amino acids are bound to each other via 1)hydrogen bonding, 2) salt bridges between acid and base groups, and 3)disulfide bonds.

At alkaline pH, the disulfide bonds in hair can be broken (Dombrink etal., Chem Matters, 1983, page 8). For example, lye-based relaxerscontain hydroxide ions which attack the disulfide linkages. Thedisruption of disulfide bonds by the lye-based relaxer is used toachieve straightening of the hair through changing of the relativepositions of opposing polypeptide chains. The straightening process iscompleted by rinsing the hair and/or application of a neutralizingcomposition.

While lye and other alkali-based relaxers are highly effective atrelaxing and straightening hair they can result in reduction of hairstrength and potential loss of hair through breakage. Relaxing hair cantherefore be viewed as a destructive and irritating process which canstrip hair of its natural fatty acids. Exposing hair to alkalineconditions also damages the hair and further causes the cuticle or outersurface of the hair strands to become roughened and can result inruffled, tangled, and generally unmanageable hair. Roughened haircatches light unevenly and makes the hair look lusterless and dull. Thehair can also be left with increased levels of static upon drying, whichcan interfere with combing and result in a condition commonly referredto as “fly-away hair.”

A variety of approaches have been developed to alleviate these problems,including post-shampoo application of hair conditioners, such asleave-on and rinse-off products. Typically, conditioning rinses put backthe oily coating, especially to the damaged portion of the hair wherethe cuticle has become ruffled since conditioners cling best to theseportions. However, too much or too heavy a conditioner will make thehair stickier, thus attracting dirt and often may make more shampooingtreatments necessary.

Yet another issue with the use of lye and other alkali-based hairrelaxers is that their application leads to completely relaxed andstraightened hair without any level of curl and/or any controllablyretained level of curl. Furthermore, due to the reduction of hairstrength and potential loss of hair due to breakage from such relaxingprocesses, any further application of a permanent wave process (i.e., tointroduce a controlled amount of curl) to the already relaxed andstraightened hair would be inadvisable as it would result in furtherdamage and/or breakage of the hair.

Thus, there is a need for hair formulations and treatments that canprovide improved conditioning benefit for hair relaxed with lye oralkali-based relaxers. Specifically, there is a need to provide longlasting moisturized feel, smooth feel, and manageability control to thetreated hair when it is dried.

There is also a need for hair formulations and treatments that repairand/or strengthen damaged hair treated with lye or alkali-based relaxingagents or hydroxide-containing relaxing agents.

There is also a need for hair formulations and treatments that affordthe ability to tune or select the level of curl achieved and/or retainedin hair which has been relaxed with lye or alkali-based relaxing agentsor hydroxide-containing relaxing agents.

Therefore, it is an object of this invention to provide improvedcompositions and methods for repairing and/or strengthening hair treatedwith lye or alkali-based relaxing agents or hydroxide-containingrelaxing agents.

It is a further object of this invention to provide compositions andmethods which can be used to tune or select the level of curl achievedand/or retained in hair that has been treated with lye or alkali-basedrelaxing agents or hydroxide-containing relaxing agents.

SUMMARY OF THE INVENTION

Compositions, kits, and methods for repairing bonds, for example,disulfide bonds, in relaxed hair that has been damaged by treatment witha lye or alkali-based relaxing agent(s) or hydroxide-containing relaxingagents. The compositions, kits, and methods can also be used to controlthe level of curl retention during the relaxing process.

Active agent formulations, which contain one or more compounds thatinteract with keratin through one or more binding events (e.g.,absorption, binding, etc.) which may involve reaction with one or morethiols in the hair are described herein. “Binding” as used herein refersto the formation of covalent, ionic, or hydrogen bonds. The active agentcompositions can provide improved conditioning and provide long lastingmoisturized feel and smooth feel without leaving the hair greasy,improve appearance (e.g., sheen), increase dry strength (tensilestrength), ease combing of the hair when wet or dried, reduce hairbreakage, or decrease frizz, or any combination thereof.

Without being bound by theory, it is believed that use of the activeagent formulations prevents reversion of the hair's repaired bonds totheir free thiol state, for at least one week, two weeks, three weeks,four weeks, one month, or two months, or longer, after application ofthe composition.

Traditional methods of straightening hair make use of lye oralkali-based relaxers or hydroxide-containing relaxing agents which canresult in reduction of hair strength and potential loss of hair throughbreakage. The methods disclosed herein use active agents which canrepair damage to relaxed hair and also provide improved methods ofstyling hair, such as during a hair relaxing/45219730 LIQ 104straightening treatment using lye or alkali-based relaxers orhydroxide-containing relaxing agents.

The active agent formulations can be applied during the hair relaxingtreatment along with the relaxing agent. Without wishing to be bound byany particular theory, the addition of the active agents describedherein simultaneously with a lye or alkali-based relaxing agent orhydroxide-containing relaxing agent can be used to tune or control thelevel of curl retention in the relaxed hair. The level of curl retentioncan depend on the amount of active agent(s) used, which can berepresented as a weight ratio of active agent present in the hairrelaxing to the amount of lye or alkali-based relaxing agent present.Typically, the greater the amount of active agent present in therelaxing formulation the greater the level of curl retention. In someembodiments, the weight ratio of the relaxing agent formulation to theactive agent formulation is in the range of about 1:10 to about 10:1.The inclusion of the one or more active agents permits not only controlof the level of curl retention during hair relaxation but further allowsfor repair of the disulfide bonds broken during the relaxation processto otherwise prevent damage caused by the relaxing agent(s).

In some other embodiments, the active agent formulations can be appliedimmediately following the application of the lye or alkali-basedrelaxing agent(s) or hydroxide-containing relaxing agents.

DETAILED DESCRIPTION OF THE INVENTION I. Definitions

Numerical ranges disclosed herein disclose individually each possiblenumber in such range, as well as any sub-ranges and combinations ofsub-ranges encompassed therein. For example, a carbon range (i.e.,C₁-C₁₀) is intended to disclose individually every possible carbon valueand/or sub-range encompassed within. For example, a carbon length rangeof C₁-C₁₀ discloses C₁, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, and C₁₀, as wellas discloses sub-ranges encompassed within, such as C₂-C₉, C₃-C₈, C₁-C₅,etc. Similarly, an integer value range of 1-10 discloses the individualvalues of 1, 2, 3, 4, 5, 6, 7, 8, and 10, as well as sub-rangesencompassed within. Further, a concentration range or weight percentrange, such as from 1% to 2% by weight of the formulation discloses, theindividual values and fractions thereof, such as 1%, 1.1%, 1.2%, 1.32%,1.48% etc., as well as sub-ranges encompassed within.

The term “hair” refers to one or more than one strand of hair, as wellas the natural components of hair, such as oil from a body. Hair alsorefers to virgin hair or processed hair, for example hair that has beenexposed to hair waving or hair straightening formulations.

An “effective amount”, e.g., of the active agent or compositionsdescribed herein, refers to an amount of the active agent in acomposition or formulation which, when applied as part of a desired hairtreatment achieves the desired result, such as curl retention,smoothness, little or no breakage, great or good feel, and/or healthyappearance by visual inspection.

“Cosmetically acceptable” refers to those compounds, materials, andcompositions, which are, within the scope of sound medical judgment,suitable for use in contact with the tissues of human beings and animalswithout excessive toxicity, irritation, allergic response, or otherproblems or complications commensurate with a reasonable benefit/riskratio. More specifically, cosmetically acceptable refers to a material,compound, or composition which is suitable for use in contact with theskin, scalp, or hair. Cosmetically acceptable materials are known tothose of ordinary skill in the art.

“Shampoo”, as used herein, generally refers to a liquid or semi-solidformulation applied to the hair that contains detergent or soap forwashing the hair.

“Conditioner”, as used herein, generally refers to a formulation (e.g.,liquid, cream, lotion, gel, semi-solid) applied to the hair to softenthe hair, smooth the hair, and/or change the sheen of the hair.

“Analog” and “Derivative” are used herein interchangeably and refer to acompound that possesses the same core as the parent compound, butdiffers from the parent compound in bond order, the absence or presenceof one or more atoms and/or groups of atoms, and combinations thereof.The derivative can differ from the parent compound, for example, in oneor more substituents present on the core, which may include one or moreatoms, functional groups, or substructures. In general, a derivative canbe imagined to be formed, at least theoretically, from the parentcompound via chemical and/or physical processes.

“Electrophilic group” or “electrophilic moiety” are used interchangeablyand refer to one or more functional groups or moieties that have anaffinity for or attract electrons.

“Michael acceptor”, as used herein, is a species of electrophilic groupsor moieties that participates in nucleophilic addition reactions. TheMichael acceptor can be or can contain an α,β-unsaturatedcarbonyl-containing group or moiety, such as a ketone. Other Michaelacceptors include pi-bonds, such as double or triple bonds conjugated toother pi-bond containing electron withdrawing groups, such as nitrogroups, nitrile groups, and carboxylic acid groups.

“Alkyl”, as used herein, refers to the radical of saturated orunsaturated aliphatic groups, including straight-chain alkyl, alkenyl,or alkynyl groups, branched-chain alkyl, alkenyl, or alkynyl groups,cycloalkyl, cycloalkenyl, or cycloalkynyl (alicyclic) groups, alkylsubstituted cycloalkyl, cycloalkenyl, or cycloalkynyl groups, andcycloalkyl substituted alkyl, alkenyl, or alkynyl groups. Unlessotherwise indicated, a straight chain or branched chain alkyl has 30 orfewer carbon atoms in its backbone (e.g., C₁-C₃₀ for straight chain,C₃-C₃₀ for branched chain), more preferably 20 or fewer carbon atoms,more preferably 12 or fewer carbon atoms, and most preferably 8 or fewercarbon atoms. In some embodiments, the chain has 1-6 carbons. Likewise,preferred cycloalkyls have from 3-10 carbon atoms in their ringstructure, and more preferably have 5, 6 or 7 carbons in the ringstructure. The ranges provided above are inclusive of all values betweenthe minimum value and the maximum value.

The term “alkyl” includes both “unsubstituted alkyls” and “substitutedalkyls”, the latter of which refers to alkyl moieties having one or moresubstituents replacing a hydrogen on one or more carbons of thehydrocarbon backbone. Such substituents include, but are not limited to,halogen, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl,or an acyl), thiocarbonyl (such as a thioester, a thioacetate, or athioformate), alkoxyl, phosphoryl, phosphate, phosphonate, aphosphinate, amino, amido, amidine, imine, cyano, nitro, azido,sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido,sulfonyl, heterocyclyl, aralkyl, or an aromatic or heteroaromaticmoiety.

Unless the number of carbons is otherwise specified, “lower alkyl” asused herein means an alkyl group, as defined above, but having from oneto ten carbons, more preferably from one to six carbon atoms in itsbackbone structure. Likewise, “lower alkenyl” and “lower alkynyl” havesimilar chain lengths. Preferred alkyl groups are lower alkyls.

The alkyl groups may also contain one or more heteroatoms within thecarbon backbone. Examples include oxygen, nitrogen, sulfur, andcombinations thereof. In certain embodiments, the alkyl group containsbetween one and four heteroatoms.

“Alkenyl” and “Alkynyl”, as used herein, refer to unsaturated aliphaticgroups containing one or more double or triple bonds analogous in length(e.g., C₂-C₃₀) and possible substitution to the alkyl groups describedabove.

“Aryl”, as used herein, refers to 5-, 6- and 7-membered aromatic rings.The ring may be a carbocyclic, heterocyclic, fused carbocyclic, fusedheterocyclic, bicarbocyclic, or biheterocyclic ring system, optionallysubstituted as described above for alkyl. Broadly defined, “Ar”, as usedherein, includes 5-, 6- and 7-membered single-ring aromatic groups thatmay include from zero to four heteroatoms. Examples include, but are notlimited to, benzene, pyrrole, furan, thiophene, imidazole, oxazole,thiazole, triazole, pyrazole, pyridine, pyrazine, pyridazine andpyrimidine. Those aryl groups having heteroatoms in the ring structuremay also be referred to as “heteroaryl”, “aryl heterocycles”, or“heteroaromatics”. The aromatic ring can be substituted at one or morering positions with such substituents as described above, for example,halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl,alkoxyl, amino, nitro, sulfhydryl, imino, amido, phosphonate,phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio, sulfonyl,sulfonamido, ketone, aldehyde, ester, heterocyclyl, aromatic orheteroaromatic moieties, —CF₃, and —CN. The term “Ar” also includespolycyclic ring systems having two or more cyclic rings in which two ormore carbons are common to two adjoining rings (the rings are “fusedrings”) wherein at least one of the rings is aromatic, e.g., the othercyclic rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, arylsand/or heterocycles, or both rings are aromatic.

“Alkylaryl”, as used herein, refers to an alkyl group substituted withan aryl group (e.g., an aromatic or hetero aromatic group).

“Heterocycle” or “heterocyclic”, as used herein, refers to a cyclicradical attached via a ring carbon or nitrogen of a monocyclic orbicyclic ring containing 3-10 ring atoms, and preferably from 5-6 ringatoms, containing carbon and one to four heteroatoms each selected fromnon-peroxide oxygen, sulfur, and N(Y) wherein Y is absent or is H, O,(C₁₋₄) alkyl, phenyl or benzyl, and optionally containing one or moredouble or triple bonds, and optionally substituted with one or moresubstituents. The term “heterocycle” also encompasses substituted andunsubstituted heteroaryl rings. Examples of heterocyclic ring include,but are not limited to, benzimidazolyl, benzofuranyl, benzothiofuranyl,benzothiophenyl, benzoxazolyl, benzoxazolinyl, benzthiazolyl,benztriazolyl, benztetrazolyl, benzisoxazolyl, benzisothiazolyl,benzimidazolinyl, carbazolyl, 4aH-carbazolyl, carbolinyl, chromanyl,chromenyl, cinnolinyl, decahydroquinolinyl, 2H,6H-1,5,2-dithiazinyl,dihydrofuro[2,3-b]tetrahydrofuran, furanyl, furazanyl, imidazolidinyl,imidazolinyl, imidazolyl, 1H-indazolyl, indolenyl, indolinyl,indolizinyl, indolyl, 3H-indolyl, isatinoyl, isobenzofuranyl,isochromanyl, isoindazolyl, isoindolinyl, isoindolyl, isoquinolinyl,isothiazolyl, isoxazolyl, methylenedioxyphenyl, morpholinyl,naphthyridinyl, octahydroisoquinolinyl, oxadiazolyl, 1,2,3-oxadiazolyl,1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, oxazolidinyl,oxazolyl, oxindolyl, pyrimidinyl, phenanthridinyl, phenanthrolinyl,phenazinyl, phenothiazinyl, phenoxathinyl, phenoxazinyl, phthalazinyl,piperazinyl, piperidinyl, piperidonyl, 4-piperidonyl, piperonyl,pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl,pyrazolyl, pyridazinyl, pyridooxazole, pyridoimidazole, pyridothiazole,pyridinyl, pyridyl, pyrimidinyl, pyrrolidinyl, pyrrolinyl, 2H-pyrrolyl,pyrrolyl, quinazolinyl, quinolinyl, 4H-quinolizinyl, quinoxalinyl,quinuclidinyl, tetrahydrofuranyl, tetrahydroisoquinolinyl,tetrahydroquinolinyl, tetrazolyl, 6H-1,2,5-thiadiazinyl,1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl,1,3,4-thiadiazolyl, thianthrenyl, thiazolyl, thienyl, thienothiazolyl,thienooxazolyl, thienoimidazolyl, thiophenyl and xanthenyl.

“Heteroaryl”, as used herein, refers to a monocyclic aromatic ringcontaining five or six ring atoms containing carbon and 1, 2, 3, or 4heteroatoms each selected from non-peroxide oxygen, sulfur, and N(Y)where Y is absent or is H, O, (C₁-C₈) alkyl, phenyl or benzyl.Non-limiting examples of heteroaryl groups include furyl, imidazolyl,triazolyl, triazinyl, oxazoyl, isoxazoyl, thiazolyl, isothiazoyl,pyrazolyl, pyrrolyl, pyrazinyl, tetrazolyl, pyridyl, (or its N-oxide),thienyl, pyrimidinyl (or its N-oxide), indolyl, isoquinolyl (or itsN-oxide), quinolyl (or its N-oxide) and the like. The term “heteroaryl”can include radicals of an ortho-fused bicyclic heterocycle of abouteight to ten ring atoms derived therefrom, particularly abenz-derivative or one derived by fusing a propylene, trimethylene, ortetramethylene diradical thereto. Examples of heteroaryl include, butare not limited to, furyl, imidazolyl, triazolyl, triazinyl, oxazoyl,isoxazoyl, thiazolyl, isothiazoyl, pyraxolyl, pyrrolyl, pyrazinyl,tetrazolyl, pyridyl (or its N-oxide), thientyl, pyrimidinyl (or itsN-oxide), indolyl, isoquinolyl (or its N-oxide), quinolyl (or itsN-oxide), and the like.

“Halogen”, as used herein, refers to fluorine, chlorine, bromine, oriodine.

The term “substituted” as used herein, refers to all permissiblesubstituents of the compounds described herein. In the broadest sense,the permissible substituents include acyclic and cyclic, branched andunbranched, carbocyclic and heterocyclic, aromatic and nonaromaticsubstituents of organic compounds. Illustrative substituents include,but are not limited to, halogens, hydroxyl groups, or any other organicgroupings containing any number of carbon atoms, preferably 1-14 carbonatoms, and optionally include one or more heteroatoms such as oxygen,sulfur, or nitrogen grouping in linear, branched, or cyclic structuralformats. Representative substituents include alkyl, substituted alkyl,alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, phenyl,substituted phenyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, halo, hydroxyl, alkoxy, substituted alkoxy, phenoxy,substituted phenoxy, aroxy, substituted aroxy, alkylthio, substitutedalkylthio, phenylthio, substituted phenylthio, arylthio, substitutedarylthio, cyano, isocyano, substituted isocyano, carbonyl, substitutedcarbonyl, carboxyl, substituted carboxyl, amino, substituted amino,amido, substituted amido, sulfonyl, substituted sulfonyl, sulfonic acid,phosphoryl, substituted phosphoryl, phosphonyl, substituted phosphonyl,polyaryl, substituted polyaryl, C₃-C₂₀ cyclic, substituted C₃-C₂₀cyclic, heterocyclic, substituted heterocyclic, aminoacid, peptide, andpolypeptide groups.

Heteroatoms, such as nitrogen, may have hydrogen substituents and/or anypermissible substituents of organic compounds described herein thatsatisfy the valences of the heteroatoms. It is understood that“substitution” or “substituted” includes the implicit proviso that suchsubstitution is in accordance with permitted valence of the substitutedatom and the substituent, and that the substitution results in a stablecompound, i.e. a compound that does not spontaneously undergotransformation such as by rearrangement, cyclization, elimination, etc.

“Polymer”, as used herein, refers to a molecule containing more than 10monomer units.

“Water-soluble”, as used herein, generally means at least 50, 75, 100,125, 150, 200, 225, or 250 g is soluble in 1 L of water at 25° C.

“Relaxing agents,” as used herein typically refers tohydroxide-containing compounds, such as lye or otherhydroxide-containing compounds, such as ammonium hydroxide. When thesehydroxide-containing compounds are present in a hair relaxingformulation the hydroxide ions produce a relaxing formulation with ahigh pH.

“Lye,” or “lye relaxer,” are used interchangeably herein and refer to anaqueous formulation or composition containing an alkali metal containinghydroxides (e.g. Sodium hydroxide and/or Potassium hydroxide).

II. Active Agent Formulations

The active agent formulations disclosed herein are concerned withtreating hair which is either in the process of being relaxed or hasundergone a relaxing treatment with a relaxing agent containingformulation. Additionally, the active agent formulations, when usedduring the relaxing treatment can be used to control, select, or tunethe level of curl achieved and/or retained in the relaxed hair, ascompared to the hair's natural unrelaxed state. The level of curlretention depends on the amount of one or more active agents applied,which can be represented as a weight ratio of the weight of one or moreactive agents (or the weight of the active agent containing formulation)to the weight of the hair relaxing formulation. Typically, the greaterthe amount of active agent present in the relaxing formulation thegreater the level of curl retention which can be achieved. Furthermore,the inclusion of one or more active agents, as described herein, permitscontrol of the level of curl retention during hair relaxation whilereducing hair breakage and damage during the relaxation process causedby the relaxing agent(s).

The formulations contain one or more active agents (also referred toherein as “compounds” or “active agents”) which can be combined with oneor more cosmetically acceptable carriers and/or excipients that areconsidered safe and effective to human hair and/or human scalp, and maybe administered to an individual's hair without causing undesirablebiological side effects, such as burning, itching, and/or redness, orsimilar adverse reactions.

The active agent is typically present in an amount ranging from about0.01 wt % to about 50 wt % of the formulation, preferably from aboutfrom about 1 wt % to about 25 wt % of the formulation, more preferablyfrom about 1 wt % to about 15 wt %, most preferably from about 1 wt % toabout 10 wt %. Typically, the active agent may be present in an amountranging from about 1 to about 5 wt % of the formulation.

The active agent is stable in aqueous solution for a period of at least2, 3, 4, 5, 6, 8, 9, 10, 11, or 12 months or longer at pH of 3 to 8,preferably 3 to 5, and a temperature of about 25-30° C., preferablyabout 25° C. “Stable” as used herein with respect to shelf-life meansthat at least 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95% of thecompound is unchanged over the specified time period.

a. Active Agent

The active agent contains at least one reactive moiety capable ofreacting with and forming bonds with a nucleophile, such as a thiol. Theactive agents optionally contain a linker group. The reactive moieties,upon reaction with thiol groups on the hair follicle, form bonds thatare stable, for example, hydrolytically stable. “Stable”, as used inreference to the bonds formed between thiol groups on hair folliclesmeans the bonds remain intact for at least one week, two weeks, threeweeks, four weeks, one month, or two months or longer when exposed towater at a pH of 3 to 8, preferably at a pH of 3 to 5, at a temperaturefrom about 5° C. to about 100° C., from about 20° C. to about 75° C.,more preferably from about 20° C. to about 50° C., from about 25° C. toabout 40° C., or from about 25° C. to about 30° C., and more preferablyat a temperature of about 25° C. In some embodiments, the temperature isabout 25° C. It is also preferred that the reaction between the reactivemoieties and thiol occur around room temperature, for example, fromabout 15° C. to about 35° C., preferably from about 20° C. to about 30°C., more preferably from about 22° C. to about 27° C.

i. Active Agents Defined by Formula I

In some embodiments, the binding agents have a structure according toFormula I:

wherein

A, B, C, and D are reactive moieties containing one or more charges,

R is a linker that contains two or more charges, wherein the charges areopposite to the charges on the reactive moieties, wherein n=1-100,preferably n=1-10, more preferably n=1; and each occurrence of p, q, r,and s is independently an integer from 0 to 25, preferably from 0 to 10,more preferably from 0 to 2. The sum of p+q+r+s is equal to or greaterthan 2.

The reactive moieties may be present on any atom of the linker. In someembodiments, the reactive moieties are the same. In some embodiments,one or more of the reactive moieties is different.

In some embodiments, the reactive moieties are negatively charged andthe linker or spacer has positively charged moieties. In otherembodiments, the reactive moieties are positively charged and the linkeror spacer has negatively charged moieties. Generally, the sum of thecharges on the binding agent of Formula I is zero though stoichiometricimbalances may exist.

The reactive moieties on the binding agents are preferably linked via alinker R. The linker R, as used herein, refers to one or morepolyfunctional, e.g. bifunctional molecules, trifunctional molecules,tetrafunctional molecules, etc., which can be used to ionically boundthe two or more reactive moieties and which do not interfere with thereactive properties of the binding agents. The reactive moieties may beattached to any part of linker R.

1. Linker R

In a preferred embodiment, in Formula I, n=1 and the linker R is not apolymer. The linker R can be a single atom, such as a heteroatom (e.g.,O or S), a group of atoms, such as a functional group (e.g., amine,—C(═O)—, —CH₂—), or multiple groups of atoms, such as an alkylene chain.Suitable linkers include but are not limited to oxygen, sulfur, carbon,boron, nitrogen, alkoxy, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl,heterocycloalkyl, heteroaryl, ether, amine, and a polymer.

The linker R is optionally independently substituted with one or moresubstituents including hydrogen, halogen, cyano, alkoxy, alkyl, alkenyl,cycloalkyl, cycloalkenyl, aryl, heterocycloalkyl, heteroaryl, amine,hydroxy, formyl, acyl, carboxylic acid (—COOH), —C(O)R¹, —C(O)OR¹,carboxylate (—COO⁻), primary amide (e.g., —CONH₂), secondary amide(e.g., —CONHR¹), —C(O)N—R₁R², —NR¹R², —NR¹S(O)₂R², NR¹C(O)R², —S(O)₂R²,—SR¹, and —S(O)₂NR¹R², sulfinyl group (e.g., —SOR¹), and sulfonyl group(e.g., —SOOR¹); wherein R¹ and R² may each independently be hydrogen,alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocycloalkyl andheteroaryl; wherein each of R¹ and R² is optionally independentlysubstituted with one or more substituents selected from the groupconsisting of halogen, hydroxyl, cyano, nitro, amino, alkylamino,dialkylamino, alkyl optionally substituted with one or more halogen oralkoxy or aryloxy, aryl optionally substituted with one or more halogenor alkoxy or alkyl or trihaloalkyl, heterocycloalkyl optionallysubstituted with aryl or heteroaryl or ═O or alkyl optionallysubstituted with hydroxyl, cycloalkyl optionally substituted withhydroxyl, heteroaryl optionally substituted with one or more halogen oralkoxy or alkyl or trihaloalkyl, haloalkyl, hydroxyalkyl, carboxy,alkoxy, aryloxy, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl anddialkylaminocarbonyl.

In some embodiments, the linker R may be an alkoxy, ether, alkyl,alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocycloalkyl, heteroaryl,amine, or a polymer.

2. Active Agents According to Formula I

The active agent according to Formula I contains at least two reactivemoieties that are capable of reacting with thiols or amines to formcovalent bonds. For example, the reactive moieties are capable ofreacting with a thiol group in the hair to form a stable covalent bond.The reactive moiety is typically an electrophilic moiety capable offorming a salt with the linker. Alternately, the reactive moiety can becapable of reacting with a free radical.

The active agent according to Formula I contains at least two reactivemoieties. However, the binding agent may contain three, four, five, six,or greater than six reactive moieties.

The reaction between the reactive moiety and the thiol groups may beinitiated at room temperature and pressure when the reactive moietycontacts a thiol group in the hair. In some embodiments, the reactionmay require an initiator, such as heat, catalyst, basic conditions, or afree radical initiator. The rate of reaction between the reactive moietyand the thiol may be increased by changes in temperature, pH, and/oraddition of one or more excipients, such as a catalyst; however, this isgenerally not required.

The two or more reactive moieties on the binding agent can be the same.In some embodiments, the two or more reactive moieties are different.

In some embodiments, the reactive moieties are capable of undergoing aconjugate additional reaction. The reactive moieties can independentlybe or contain a Michael acceptor, a succinimidyl-containing group, amaleimido-containing group, azlactone, a benzoxazinone derivative, vinylsulfone, vinyl sulfoximine, vinyl sulfonate, vinyl phosphonate,benzoxazinone, isocyanate, epoxide, an electrophilic moiety containing aleaving group, an electrophilic thiol acceptor, acrylic or acrylategroup, a methacrylic or methacrylate group, a styrene group, an acrylamide group, a methacryl amide group, a maleate group, a fumarate group,an itaconate group, a vinyl ether group, an allyl ether group, an allylester group, a vinyl ester group, a sulfonate group, a phosphonategroup, a sulfoxide group, a sulfonamide group, a sulfinimide group, asulfinamide group, a sulfonimidate group, or a sulfonimidamide group.

In the preferred embodiments, each of reactive moieties A, B, C, and/orD when present independently contains a moiety selected from the groupconsisting of a vinyl sulfone, an acrylate group, a methacrylate group,a styrene group, an acryl amide group, a methacryl amide group, amaleate group, a fumarate group, and an itaconate group. Further, in thepreferred embodiments, n=1 and the linker R is not a polymer.Optionally, all of the reactive moieties are the same. For example, insome embodiments all of the reactive moieties are maleate groups.

In some embodiments, the active agent according to Formula I has one ofthe following structures:

Active agents according to Formula I are further described in U.S.Patent Publication No. 2015/0034117 A1 to Pressly, et al. and issued asU.S. Pat. No. 9,095,518, which is incorporated herein by reference withrespect to its disclosure of active agents.

ii. Active Agents Defined by Formula II

In some other embodiments, the active agent is a polyfunctional compoundthat contains ionizable functional groups capable of forming ionic bondsand functional groups capable of forming a covalent bond with anucleophile, such as a thiol or an amine. Suitable ionizable functionalgroups include, but are not limited to, acidic groups such as carboxylicacids, sulfonic acids, phosphonic acids, and basic groups, such asamines. Suitable functional groups capable of forming a covalent bondwith a nucleophile, such as a thiol or an amine, include, but are notlimited to, Michael acceptors, alkyl halides or sulfonate esters.

The active agent may have the following Formula II:

wherein Z is a linker or is absent, m and n are each an integerindependently selected from 1-6, provided that m+n is at least 2, B is afunctional group capable of forming a covalent bond with a thiol oramine group, and A is an ionizable functional group. Preferably, thelinker Z is not a polymer.

Exemplary active agents according to Formula II may contain thiolreactive functional groups, as group B, for example, such as those shownin the following moieties:

wherein R is independently selected from hydrogen, C₁₋₆ alkyl, aryl, oran ionizable functional group; Z′ is oxygen (O), NH, or is absent; and Gis carbon (C) and g is 1, or G is sulfur (S) and g is 2. In preferredembodiments, Z is a linker or is absent, the linker is not a polymer,and group B is a functional group capable of forming a covalent bondwith a thiol or amine group and group B is independently selected fromthe group consisting of:

wherein R, Z′, G, and g are as previously defined.

1. Linker Z

The linker Z, when present, can be or can contain an alkyl, alkenyl,cycloalkyl, cycloalkenyl, aryl, heterocycloalkyl or heteroaryl group.One or more of the carbon atoms in the alkyl, alkenyl, cycloalkyl,cycloalkenyl, and aryl groups can be substituted with a heteroatom,yielding, for instance, an ether or alkylamine-containing linker.

The linker Z may optionally be substituted with one or moresubstituents, which may be the same or different, including hydrogen,halogen, cyano, alkoxy, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl,heterocycloalkyl, heteroaryl, amine, hydroxy, oxo, formyl, acyl,carboxylic acid (—COOH), —C(O)R¹, —C(O)OR¹, carboxylate (—COO—), primaryamide (e.g., —CONH₂), secondary amide (e.g., —CONHR₁₁), —C(O)NR¹R²,—NR¹R², —NR¹S(O)₂R², —NR¹C(O)R²—S(O)₂R²—SR¹, and —S(O)₂NR¹R², sulfinylgroup (e.g., —SOR₁), and sulfonyl group (e.g., —SOOR₁); wherein R¹ andR² may each independently be hydrogen, alkyl, alkenyl, alkynyl,cycloalkyl, aryl, heterocycloalkyl and heteroaryl; wherein each of R¹and R² is optionally independently substituted with one or moresubstituents selected from the group consisting of halogen, hydroxyl,oxo, cyano, nitro, amino, alkylamino, dialkylamino, alkyl optionallysubstituted with one or more halogen or alkoxy or aryloxy, aryloptionally substituted with one or more halogen or alkoxy or alkyl ortrihaloalkyl, heterocycloalkyl optionally substituted with aryl orheteroaryl or oxo or alkyl optionally substituted with hydroxyl,cycloalkyl optionally substituted with hydroxyl, heteroaryl optionallysubstituted with one or more halogen or alkoxy or alkyl or trihaloalkyl,haloalkyl, hydroxyalkyl, carboxy, alkoxy, aryloxy, alkoxycarbonyl,aminocarbonyl, alkylaminocarbonyl and dialkylaminocarbonyl.

In certain preferred embodiments, the linker Z is a C₁₋₁₀ alkyl groupwhich may be unsubstituted or substituted one or more times by oxo,hydroxyl, carboxyl, amido or amino. Preferably, the linker Z is a C₁₋₄alkyl group. The alkyl group may be linear or branched. The alkyl groupmay also be interrupted one or more times by a heteroatom selected fromoxygen, sulfur and nitrogen. An example of such a di-carboxylic acidshaving a heteroatom interruption is thiodipropionic acid. In otherembodiments, the alkyl group may contain one or more double or triplebonds.

In some embodiments, the active agent according to Formula II has one ofthe following structures:

or is a simple salt of these structures.

iii. Active Agents Defined by Formula III

In certain other embodiments, the active agent may have the followingFormula III:

wherein Z is a linker or is absent, m and n are each an integerindependently selected from 1-6, provided that m+n is at least 2, B is afunctional group capable of forming a covalent bond with a nucleophile,such as a thiol or amine group, A is an ionizable functional group asdefined above, and C is an ionic group which is also capable of forminga covalent bond with a thiol and which has a charge opposite to that ofionizable group A. Group C is ionically bonded (denoted by dashed line)to group A. For ionic group C, o is an integer value independentlyselected from 1-6, such that the sum of charges of group C and ionizablegroup A is zero. Preferably linker Z is not a polymer.

In active agents of Formula III, group C is an ionic group which isionically bonded to ionizable group A and contains at least one thiolreactive. Group C may be a Michael acceptor, a succinimidyl-containinggroup, a maleimido-containing group, azlactone, a benzoxazinonederivative, vinyl sulfone, vinyl sulfoximine, vinyl sulfonate, vinylphosphonate, benzoxazinone, isocyanate, epoxide, an electrophilic moietycontaining a leaving group, an electrophilic thiol acceptor, acrylic oracrylate group, a methacrylic or methacrylate group, a styrene group, anacryl amide group, a methacryl amide group, a maleate group, a fumarategroup, an itaconate group, a vinyl ether group, an allyl ether group, anallyl ester group, a vinyl ester group, a sulfonate group, a phosphonategroup, a sulfoxide group, a sulfonamide group, a sulfinimide group, asulfinamide group, a sulfonimidate group, or a sulfonimidamide group.

The active agents according to Formula III may contain thiol reactivefunctional groups which react with a nucleophile, such as a thiol, asgroup B. Exemplary thiol reactive functional groups include, but are notlimited, to those shown in the following moieties:

wherein R is independently selected from hydrogen, C₁₋₆ alkyl, aryl, oran ionizable functional group; Z′ is oxygen (O), NH, or is absent; and Gis carbon (C) and g is 1, or G is sulfur (S) and g is 2. In preferredembodiments, Z is a linker or is absent, the linker is not a polymer,and group B is a functional group capable of forming a covalent bondwith a thiol or amine group and group B is independently selected fromthe group consisting of:

wherein R, Z′, G, and g are as previously defined.

1. Linker Z

The linker Z, when present, can be or can contain an alkyl, alkenyl,cycloalkyl, cycloalkenyl, aryl, heterocycloalkyl or heteroaryl group.One or more of the carbon atoms in the alkyl, alkenyl, cycloalkyl,cycloalkenyl, and aryl groups can be substituted with a heteroatom,yielding, for instance, an ether or alkylamine-containing linker.

The linker Z may optionally be substituted with one or moresubstituents, which may be the same or different, including hydrogen,halogen, cyano, alkoxy, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl,heterocycloalkyl, heteroaryl, amine, hydroxy, oxo, formyl, acyl,carboxylic acid (—COOH), —C(O)R¹, —C(O)OR¹, carboxylate (—COO—), primaryamide (e.g., —CONH₂), secondary amide (e.g., —CONHR₁₁), —C(O)NR¹R²,—NR¹R², —NR¹S(O)₂R², —NR¹C(O)R², —S(O)₂R²—SR¹, and —S(O)₂NR¹R², sulfinylgroup (e.g., —SOR₁), and sulfonyl group (e.g., —SOOR₁); wherein R¹ andR² may each independently be hydrogen, alkyl, alkenyl, alkynyl,cycloalkyl, aryl, heterocycloalkyl and heteroaryl; wherein each of R¹and R² is optionally independently substituted with one or moresubstituents selected from the group consisting of halogen, hydroxyl,oxo, cyano, nitro, amino, alkylamino, dialkylamino, alkyl optionallysubstituted with one or more halogen or alkoxy or aryloxy, aryloptionally substituted with one or more halogen or alkoxy or alkyl ortrihaloalkyl, heterocycloalkyl optionally substituted with aryl orheteroaryl or oxo or alkyl optionally substituted with hydroxyl,cycloalkyl optionally substituted with hydroxyl, heteroaryl optionallysubstituted with one or more halogen or alkoxy or alkyl or trihaloalkyl,haloalkyl, hydroxyalkyl, carboxy, alkoxy, aryloxy, alkoxycarbonyl,aminocarbonyl, alkylaminocarbonyl and dialkylaminocarbonyl.

In certain preferred embodiments, the linker Z is a C₁₋₁₀ alkyl groupwhich may be unsubstituted or substituted one or more times by oxo,hydroxyl, carboxyl, amido or amino. Preferably, the linker Z is a C₁₋₄alkyl group. The alkyl group may be linear or branched. The alkyl groupmay also be interrupted one or more times by a heteroatom selected fromoxygen, sulfur and nitrogen. An example of such a di-carboxylic acidshaving a heteroatom interruption is thiodipropionic acid. In otherembodiments, the alkyl group may contain one or more double or triplebonds.

In some embodiments, the active agent of Formula III has one of thefollowing structures:

b. Excipients

The active agent formulations can typically contain one or morecosmetically acceptable excipients. Cosmetically acceptable excipientsinclude, but are not limited to, water, preservatives, antioxidants,chelating agents, sunscreen agents, vitamins, dyes, hair coloringagents, proteins, amino acids, natural extracts such as plant extracts,humectants, fragrances, perfumes, oils, emollients, lubricants, butters,penetrants, thickeners, viscosity modifiers, polymers, resins, hairfixatives, film formers, surfactants, detergents, emulsifiers,opacifying agents, volatiles, propellants, liquid vehicles, carriers,salts, pH adjusting agents (e.g., citric acid), neutralizing agents,buffers, hair conditioning agents, anti-static agents, anti-frizzagents, anti-dandruff agents, absorbents, and combinations thereof.

The formulations may contain one or more cosmetically acceptableexcipients. In some forms, the formulations contain the active agent,water, and optionally a preservative and/or fragrance.

The formulation for treating hair during or immediately following arelaxation process with a relaxing formulation may be in any suitablephysical form. Suitable forms include, but are not limited to low tomoderate viscosity liquids, lotions, milks, mousses, sprays, gels,creams, shampoos, conditioners, and the like. Suitable excipients, suchas those listed above, are included or excluded from the hair careformulation depending on the form of use of the formulation (e.g., hairspray, cream, conditioner, or shampoo).

The cosmetically acceptable excipient is typically present in an amountranging from about 10 wt % to about 99.99 wt % of the formulation,preferably about 40 wt % to about 99 wt %, more preferably from about 80wt % to about to about 99 wt %.

i. Surfactants

Surfactants are surface-active agents that are able to reduce thesurface tension of water and cause the formulation to slip across oronto the hair. Surfactants may also include detergents and soap. Thesurfactants may be amphoteric, anionic, or cationic. Suitablesurfactants that may be used in the formulation include, but are notlimited to, 3-aminopropane sulfonic acid, almond amide, almondamidopropyl betaine, almond amidopropylamine oxide, aluminumhydrogenated tallow glutamate, aluminum lanolate, aminoethyl sulfate,aminopropyl lauryl glutamine, ammonium C₁₂₋₁₅ alkyl sulfate, ammoniumC₁₂₋₁₅ pareth sulfate, ammonium C₁₂₋₁₆ alkyl sulfate, ammonium C₆₋₁₀perfluoroalkylsulfonate, ammonium capryleth sulfate, ammoniumcapryleth-3 sulfate, ammonium monoglyceride sulfate, ammonium sulfate,ammonium isothionate, ammonium cocoyl sarcosinate, ammonium cumenesulfonate, ammonium dimethicone copolyol sulfate, ammoniumdodecylbenzenesulfonate, ammonium isostearate, ammonium laureth sulfate,ammonium laureth-12 sulfate, ammonium laureth-5 sulfate, ammoniumlaureth-6 carboxylate, ammonium laureth-7 sulfate, ammonium laureth-8carboxylate, ammonium laureth-9 sulfate, ammonium lauroyl sarcosinate,ammonium lauryl sulfate, ammonium lauryl sulfosuccinate, ammonium myrethsulfate, ammonium myristyl sulfate, ammonium nonoxynol-30 sulfate,ammonium nonoxynol-4 sulfate, ammonium oleate, ammonium palm kernelsulfate, ammonium polyacrylate, ammonium stearate, ammonium tallate,ammonium xylene sulfonate, ammonium xylene sulfonate, amp-isostearoylgelatin/keratin amino acids/lysine hydroxypropyltrimonium chloride,amp-isostearoyl hydrolyzed collagen, apricot kernel oil PEG-6 esters,apricot amide, apricot amidopropyl betaine, arachideth-20, avocadamide,avocadamidopropyl betaine, babassuamide, babassuamidopropyl betaine,babassuamidopropylamine oxide, behenalkonium chloride, behenamide,behenamide, behenamidopropyl betaine, behenamine oxide, sodium laurethsulfate, sodium lauryl sulfate, a polyoxyether of lauryl alcohol orceteareth-20, or combinations thereof.

Suitable anionic surfactants include, but are not limited to, thosecontaining carboxylate, sulfonate and sulfate ions. Examples of anionicsurfactants include sodium, potassium, ammonium of long chain alkylsulfonates and alkyl aryl sulfonates such as sodium dodecylbenzenesulfonate; dialkyl sodium sulfosuccinates, such as sodium dodecylbenzenesulfonate; dialkyl sodium sulfosuccinates, such as sodiumbis-(2-ethylthioxyl)-sulfosuccinate; and alkyl sulfates such as sodiumlauryl sulfate. Cationic surfactants include, but are not limited to,quaternary ammonium compounds such as benzalkonium chloride,benzethonium chloride, cetrimonium bromide, stearyl dimethylbenzylammonium chloride, polyoxyethylene and coconut amine. Examples ofnonionic surfactants include ethylene glycol monostearate, propyleneglycol myristate, glyceryl monostearate, glyceryl stearate,polyglyceryl-4-oleate, sorbitan acylate, sucrose acylate, PEG-150laurate, PEG-400 monolaurate, polyoxyethylene monolaurate, polysorbates,polyoxyethylene octylphenylether, PEG-1000 cetyl ether, polyoxyethylenetridecyl ether, polypropylene glycol butyl ether, Poloxamer® 401,stearoyl monoisopropanolamide, and polyoxyethylene hydrogenated tallowamide. Examples of amphoteric surfactants include sodiumN-dodecyl-.beta.-alanine, sodium N-lauryl-β-iminodipropionate,myristoamphoacetate, lauryl betaine and lauryl sulfobetaine.

More than one surfactant may be included in the formulation.

The surfactants are optionally included in an amount ranging from about0.1% to about 15% by weight of the formulation, preferably about 1% toabout 10% by weight of the formulation.

ii. Emollients

Emollient refers to a material that protects against wetness orirritation, softens, soothes, coats, lubricates, moisturizes, protects,and/or cleanses the skin. Suitable emollients for use in theformulations include, but are not limited to a silicone compound (e.g.,dimethicone, cyclomethicone, dimethicone copolyol or a mixture ofcyclopentasiloxane and dimethicone/vinyldimethicone cross polymer,cyclopentasiloxane polysilicone), polyols such as sorbitol, glycerin,propylene glycol, ethylene glycol, polyethylene glycol, caprylyl glycol,polypropylene glycol, 1,3-butane diol, hexylene glycol, isoprene glycol,xylitol; ethylhexyl palmitate; a triglyceride such as caprylic/caprictriglyceride and fatty acid ester such as cetearyl isononanoate or cetylpalmitate. In a specific embodiment, the emollient is dimethicone,amidodimethicone, dimethiconol, cyclopentasiloxane, potassiumdimethicone PEG-7 panthenyl phosphate, or a combination thereof. Morethan one emollient may be included in the formulation.

The emollient is optionally included in an amount ranging from about0.5% to about 15% by weight of the formulation, preferably from about 1%to about 10% by weight of the formulation.

iii. Emulsifiers

The formulations may also contain one or more emulsifiers. Suitableemulsifiers include, but are not limited to, copolymers of anunsaturated ester and styrene sulfonate monomer, cetearyl alcohol,glyceryl ester, polyoxyethylene glycol ether of cetearyl alcohol,stearic acid, polysorbate-20, ceteareth-20, lecithin, glycol stearate,polysorbate-60, or polysorbate-80, or combinations thereof. More thanone emulsifier may be included in the formulation.

The emulsifier is optionally included in an amount ranging from about0.05% to about 15% by weight of the formulation, preferably from about0.1% to about 10% by weight of the formulation.

iv. Preservatives

One or more preservatives may be included in the formulations to preventmicrobial growth in the formulations. Suitable preservatives include,but are not limited to, glycerin containing compounds (e.g., glycerin orethylhexylglycerin or phenoxyethanol), benzyl alcohol, parabens(methylparaben, ethylparaben, propylparaben, butylparaben,isobutylparaben, etc.), sodium benzoate, ethylenediamine-tetraaceticacid (EDTA), potassium sorbate, and/or grapefruit seed extract, orcombinations thereof. More than one preservative may be included in theformulation. Other preservatives are known in the cosmetics industriesand include salicylic acid, DMDM Hydantoin, Formaldehyde, Chlorphenism,Triclosan, Imidazolidinyl Urea, Diazolidinyl Urea, Sorbic Acid,Methylisothiazolinone, Sodium Dehydroacetate, Dehydroacetic Acid,Quaternium-15, Stearalkonium Chloride, Zinc Pyrithione, SodiumMetabisulfite, 2-Bromo-2-Nitropropane, Chlorhexidine Digluconate,Polyaminopropyl biguanide, Benzalkonium Chloride, Sodium Sulfite, SodiumSalicylate, Citric Acid, Neem Oil, Essential Oils (various), LacticAcid, and Vitamin E (tocopherol).

The preservative is optionally included in an amount ranging from about0.1% to about 5% by weight of the formulation, preferably from about0.3% to about 3% by weight of the formulation. Preferably, theformulations are paraben free.

v. Conditioning Agents

One or more conditioning agents may be included in the formulations.Suitable conditioning agents include, but are not limited to,silicone-based agents (e.g., silicone quaternium-8), panthenol,hydrolyzed wheat and/or soy protein, amino acids (e.g. wheat aminoacids), rice bran wax, meadowfoam seed oil, mango seed oil, grape seedoil, jojoba seed oil, sweet almond oil, hydroxyethyl behenamidopropyldimonium chloride, aloe leaf extract, aloe barbadensis leaf juice,phytantriol, panthenol, retinyl palmitate, behentrimonium methosulfate,cyclopentasiloxane, quaternium-91, stearamidopropyl dimethylamine, andcombinations thereof.

The conditioning agent(s) is optionally included in an amount rangingfrom about 0.1% to about 5% by weight of the formulation, preferablyfrom about 0.3% to about 3% by weight of the formulation.

vi. Diluents

Diluent, as used herein, refers to a substance(s) that dilutes theactive agent. Water is the preferred diluent. The formulations typicallycontains greater than one percent (wt) water, preferably greater thanfive percent (wt) water, more preferably greater than 50% (wt) water,and most preferably greater than 80% (wt) water. Alcohols, such as ethylalcohol and isopropyl alcohol, may be used at low concentrations (about0.5% by weight of the formulation) to enhance hair or skin penetrationand/or reduce odor.

vii. Viscosity Modifying Agents

The formulations may contain one or more viscosity modifying agents,such as viscosity increasing agents. Classes of such agents include, butare not limited to, viscous liquids, such as polyethylene glycol,semisynthetic polymers, such as semisynthetic cellulose derivatives,synthetic polymers, such as carbomers, poloxamers, andpolyethyleneimines (e.g., PEI-10), naturally occurring polymers, such asacacia, tragacanth, alginates (e.g., sodium alginate), carrageenan,vegetable gums, such as xanthan gum, petroleum jelly, waxes, particulateassociate colloids, such as bentonite, colloidal silicon dioxide, andmicrocrystalline cellulose, surfactants, such as PPG-2 hydroxyethylcoco/isostearamide, emulsifiers, such as disteareth-75 IPDI, and salts,such as sodium chloride, and combinations thereof.

viii. Antioxidants

The formulations may contain one or more antioxidants. Examples include,but are not limited to, tocopheryls, BHT, ascorbic acid, Camelliasinensis leaf extract, ascorbyl palmitate, magnesium ascorbyl phosphate,carotenoids, resveratrol, triethyl citrate, arbutin, kojic acid,tetrahexydecyl ascorbate, superoxide dismutase, zinc, sodiummetabisulfite, lycopene, ubiquinone, and combinations thereof.

ix. Opacifying Agents

The formulations may contain one or more opacifying agents. Opacifyingagents are added to the formulations to make them opaque. Suitableopacifying agents include, but are not limited to, glycol distearate andethoxylated fatty alcohols.

c. Forms of the Formulation

i. Creams

The formulation may be in the form of a cream. The cream typicallyincludes the active agent in a suitable carrier. The active agent may beincluded in any suitable concentration. Typical concentrations of theactive agent in the cream range from small amounts such as approximately0.01% (wt), preferably at least 0.1% (wt), to large amounts, such as upto 50% (wt). Preferably the cream contains the active agent in aconcentration ranging from 0.1% (wt) to 5% (wt), more preferably from0.1% wt to 3% (wt). While greater concentrations of active agent couldbe present in the cream, they are generally not needed to achieve thedesired results.

Additionally, the cream may include an oil, a hair conditioning agent,and/or a thickening agent. The cream may also include a fragrance, aplant extract, and/or a surfactant. The cream may be packaged in a tube,tub, bottle, or other suitable container.

ii. Liquid Active Agent Formulations

In some embodiments, a liquid active agent formulation is provided,which is mixed at the time of use with a second formulation, such as forrelaxing hair. In these embodiments, the liquid active agent formulationmay contain any suitable concentration of active agent in a suitablecarrier, typically a diluent, such as described above. The concentrationof the active agent is suitable to provide a mixture with theappropriate final volume and final concentration of active agent, asdesired.

For example, a liquid active agent formulation can contain aconcentration of active agent ranging from about 5% (wt) to about 50%(wt) or greater. In a preferred embodiment, the liquid active agentformulation contains about 5% (wt) to 20% (wt) active agent.

For straightening applications, prior to use, a sufficient volume of aliquid active agent formulation is mixed with a sufficient volume of arelaxing agent-containing formulation to form a relaxing/straighteningmixture having the desired concentration of active agent. Typicalconcentrations of the active agent in the relaxing mixture can rangefrom small amounts, such as approximately at least 0.01% (wt),preferably at least 0.1% (wt), to large amounts, such as up to 50% (wt).Preferably the relaxing mixture contains the active agent in aconcentration ranging from 0.1% (wt) to 5% (wt), more preferably from 1%wt to 5% (wt).

III. Relaxing Formulations

A relaxing formulation contains one or more relaxing agents forstraightening hair. Without being bound by theory, it is believed thatthe hydroxide ions in the relaxing agents attack disulfide linkages inhair and producing reduced thiol groups. The disruption of disulfidebonds by the relaxing agents is used to achieve straightening of thehair through changing of the relative positions of opposing polypeptidechains. Relaxing agent formulations and their methods of preparation areknown in the art.

Exemplary relaxing agents include lye, alkali-based, orhydroxide-containing agents which include, but are not limited, toalkali metal hydroxides such as sodium hydroxide, lithium hydroxide, andpotassium hydroxide. In some other embodiments, the relaxing agent isammonium hydroxide. Hydroxide-containing relaxing agents are known tothose of skill in the art. Hydroxide-containing relaxers arecommercially available, such as from the following commercial brands:Mizani® Rhelaxer, Design Essentials®, and Dudley's Q®.

IV. Kits

Kits for relaxing hair or treating relaxed hair typically contain anactive agent formulation containing an effective amount of an activeagent.

Instructions for use of the kit are also typically provided.

The kit may further contain a formulation, also referred to herein asthe relaxing formulation, capable of disrupting the disulfide bonds inthe hair and producing reduced thiol groups during a relaxing process.

The relaxing agent and active agent formulations are typically providedseparately and instructions are provided for simultaneously applying therelaxing agent and active agent formulations to the hair. For example,the instructions may provide for creating a mixture of the relaxingagent and active agent formulations, and then applying the mixture tothe hair. Alternatively, the instructions may provide for applying therelaxing agent to the hair simultaneously while applying the activeagent formulation to the hair (but not as a mixture). The instructionsmay also include instructions for how to select the desired amount ofactive agent to be used, such as by specifying a volume or mass (orrange thereof) of the active agent or active agent formulation, thedesired weight ratio of active agent to relaxing agent, and/or thedesired weight ratio of first relaxing formulation to second activeagent-containing formulation in order to control the level of curlretention in the relaxed hair.

Alternatively, instructions are provided for first applying the relaxingagent to the hair and subsequently applying the active agent formulationto the hair. The instructions may explain the amount of time (i.e., inthe range of about one second to about 30 minutes, more preferablywithin about 60 seconds) that can pass following the application of therelaxing formulation before the application of the active agentformulation and/or the amount of active agent formulation to be appliedin order to control the level of curl retention in the hair. Theinstructions may also include instructions for how to select the desiredamount of active agent to be used, such as by specifying a volume ormass (or range thereof) of the active agent or active agent formulation,the desired weight ratio of active agent to relaxing agent, and/or thedesired weight ratio of first relaxing formulation to second activeagent-containing formulation in order to control the level of curlretention in the relaxed hair.

A. Relaxing Formulation

In some embodiments, the kit contains a relaxing formulation, whichcontains one or more relaxing agents for straightening hair as describedherein. Hydroxide-containing relaxing agents are well-known to those ofskill in the art.

B. Active Agent Formulation

The active agent formulation contains one or more active agents asdescribed herein. Suitable formulations containing the active agents arediscussed above. The active agent formulations may be in any suitableform. Suitable forms include, but are not limited to, low to moderateviscosity liquids, lotions, gels, creams, and the like. In certainembodiments, the active agent formulation is a liquid, lotion, or creamof sufficient viscosity which can be mixed with a formulation containingone or more relaxing agents. The active agent formulation is provided ina suitable container, which depends on the form of the formulation.

In one embodiment, the active agent formulation is provided as two ormore separate ingredients. For example, the active agent may be providedas a dry powder in a sealed package and the excipient provided in a vialor other container. A suitable mixing container for the active agent andthe excipient may be provided.

c. Other Materials in the Kit

The kit may further contain an odor eliminator. The odor eliminator canbe incorporated into the reducing formulation. Alternately, the odoreliminator is present in a suitable container for use before or afterwashing the active formulation from the hair. Suitable odor eliminatorsare known to those of ordinary skill in the art.

IV. Methods of Use

Methods for treating hair during or immediately following a relaxingprocess are described herein. In some embodiments, the methods includecontrolling, selecting, or tuning the level of curl achieved and/orretained during a hair relaxation treatment (with a relaxingformulation) by controlling the relative amount of active agentformulation to the amount of relaxing agent formulation used in acombined formulation containing both components.

In some embodiments, the method for treating hair involves applying afirst formulation to the hair containing one or more relaxing agents andapplying a second formulation to the hair comprising one or more activeagents of Formula I, II, and/or III, as described above.

These methods produce hair with reduced damage or breakage, compared toa treatment of the hair with relaxing agent(s) alone. Further the amountof the one or more active agents of the second formulation is effectiveto retain a level of curl, which can be expressed as percent curlretention, in the treated hair.

A. Treatment of Hair During or Following a Hydroxide Relaxing Process

The first step in straightening hair is breaking bonds in the hair. Theprocess for breaking the bonds results from the application of a causticagent. The process for applying a relaxing agent in normal hairstraightening procedures is known to those skilled in the art. Forexample, to relax or straighten hair, the hair is first washed. Second,a formulation containing one or more relaxing agents, such as a sodiumhydroxide-containing solution or lotion, is applied to the hair. Thehair is allowed to set for a specified period of time, and then therelaxing formulation is rinsed from the hair. Optionally, a neutralizingformulation may be applied to the relaxed hair.

In one embodiment, the active agents described herein can be applied tothe hair during the relaxation process. Preferably, the active agent isapplied simultaneously with the relaxing agent(s) during thestraightening process. In some other embodiments, the active agent canbe applied immediately following the application of the relaxingformulation, whether the relaxing formula is rinsed out or not. Theactive agent formulation is typically applied the same day (i.e. within24 hours) as the relaxing formulation is applied.

a. Rinse or Wash the Hair

Optionally, the hair may be shampooed and/or conditioned prior toapplying the active agent formulation. Alternately, the hair may only beneutralized and/or rinsed with water prior to application of the activeagent formulation.

b. Apply the Active Agent Formulation to the Hair

The active agent formulation is applied to the hair eithersimultaneously during the relaxation process (i.e., in combination withthe relaxing agent-containing formulation) or is applied immediatelyfollowing the application of the relaxing agent formulation or,alternatively, applied at a short interval of time immediately followingthe application of the relaxing formulation. “Short interval,” as usedherein, refers to a period of time in the range of one second to 30minutes, one minute to 20 minutes, or 5 minutes to 15 minutes. Incertain other embodiments, the active agent formulation is appliedwithin the same day following application/treatment of the hair with therelaxing formulation.

In some embodiments, a first formulation containing one or more relaxingagent(s) and a second formulation containing one or more active agent(s)are combined, mixed and applied to the hair as a single combinedformulation containing both types of agents to the hair undergoing arelaxing/straightening process. In some embodiments, the weight ratio ofrelaxing agent(s) to active agent(s) in the combined formulation isselected to control and retain a particular level of curl, which can beexpressed as percent curl retention, in the hair as compared to thehair's unrelaxed (e.g. natural) amount of curl. Typically, the lower theamount of active agent(s) relative to the amount of relaxing agents thegreater the extent of straightening. Conversely, the higher the amountof active agent(s) to relaxing agent(s) present in the combinedformulation the greater the level of retention of curl. Similarly, inother embodiments, the level of curl retained in the treated hair isdetermined by the amount of the active agent(s) present in the secondformulation, where the amount of active agent(s) used is lower for alower percentage of curl retention than the amount of active agent(s)used for a higher percentage of curl retention. Accordingly, it ispossible to tune the level of curl retained in hair that is treated withlye or alkali-based relaxing agents or hydroxide-containing relaxingagents by applying a selected amount of the one or more active agent(s).

In some embodiments, the weight ratio of the first formulationcontaining relaxing agent(s) to the second formulation containing activeagent(s) is in the range of about 1:99 to about 99:1, more preferablyabout 10:1 to about 1:10 and the weight ratio is effective to retain alevel of the hair's unrelaxed and natural curl (i.e. before relaxingtreatment). The weight ratio may be about 10:1, 9:1, 8:1, 7:1, 6:1, 5:1,4:1, 3:1, 2:1 or 1:1 of the first formulation to the second formulation.In some preferred embodiments, the weight ratio of the first formulationto the second formulation is 8:1. In other preferred embodiments, theweight ratio of the first formulation to the second formulation is 4:1.These ratios are particularly useful with commercially availablerelaxing agents, such as Mizani® Rhelaxer, as shown in the Examples. Theamount of the second formulation containing active agent(s) and theconcentration of the active agent(s) present therein can be varied asneeded when using other relaxing agents to achieve similar results.Commercially available hydroxide-based relaxer formulations typicallyhave a pH of about 12 to 14, representing a difference in hydroxide ionconcentration of about 100 times between the ends of the range. Thus,the amount of active agent(s) can be varied as a function of the pH ofthe relaxing formulation being used, and can be further adjustedaccording to the buffering capacity of each relaxer, if a bufferingagent is present.

In yet other embodiments, the weight ratio of the first formulationcontaining relaxing agent(s) to the weight of active agent(s) is in therange of about 1:99 to about 99:1, more preferably about 10:1 to about1:10 and the weight ratio is effective to retain a level of the hair'sunrelaxed and natural curl (i.e. before relaxing treatment). In somepreferred embodiments, the weight ratio of the first formulation to theweight of the active agent(s) is 40:1. In other preferred embodiments,the weight ratio of the first formulation to the weight of the activeagent(s) is 20:1.

As used herein, “percent curl retention” and “percentage of curlretention” are used interchangeably to refer to the level of curl thatis retained following a treatment, as compared to the hair's unrelaxedand natural amount of curl (i.e. prior to treatment with a relaxingagent). One exemplary method for determining percent curl retention oftreated hair (e.g. a swatch of hair) is based on the followingcalculation using the formula:

Percent Curl Retention (L_(ext)−L_(f))/(L_(est)−L_(i))×100

where L_(ext) is the length of hair prior to treatment when fullyextended, L_(f) is the final (non-extended) length of the hair followinga treatment, and L_(i) is the initial (non-extended) length of hair inits initial (i.e. unrelaxed) state with its natural amount of curl, andwhere L_(ext) does not equal L_(i). For example, the level of curl(percent curl retention) to be retained following treatment with theactive agent(s) and relaxing agent(s) can be in the range of about0-99%, more preferably less than about 90%, more preferably less thanabout 80%, more preferably less than about 70%, more preferably lessthan about 60%, more preferably less than about 50%. In certainembodiments, the level of curl retained is between 0% and 10%. In otherembodiments, the percent curl retention is greater than 50%.

In embodiments where the hair is straightened with little to no curlremaining in the hair, the level of curl retaining is less than about10%, such as from about 10% to 0%, from about 5% to 0%, or from about 1%to 0%.

The percent of curl retention of the hair following treatment can bemaintained with no appreciable or substantially (i.e., less than about5%, 4%, 3%, 2%, or 1%) no appreciable change in its level of curl for aperiod of time in the range of one week to six months, more preferablytwo weeks to four months, and most preferably one month to three months.In some embodiments, the percentage of curl retention can be maintainedfor at least about one week, two weeks, three weeks, four weeks, onemonth, two months, three months, four months, five months, six months,or longer.

In some embodiments, the active agent-containing second formulation isis applied to the hair immediately after the application of a firstrelaxing agent-containing formulation, while in other embodiments ashort interval of time is permitted to pass prior to application of theactive agent containing formulation (e.g. 10, 15, 25, 30, 45, or 60seconds or longer following relaxing formulation application). The hairbeing treated does not have to be washed or rinsed prior to theapplication of the active agent containing formulation. In someembodiments, the intervening period of time between the application ofthe relaxing agent(s) and the subsequent application of the active agentformulation and/or the amount of active agent formulation applied to therelaxing hair can be used to control the percent curl retention in therelaxed hair. In some embodiments, the amount of time between theapplication of the relaxing agent containing formulation and theapplication of the active agent containing formulation can be selectedto achieve a desired amount or range of percent curl retention.

In some embodiments, the active agent formulation may be applied in asingle application, or application may be repeated one or more times asneeded. Typically, the amount of active agent formulation applied issufficient to saturate the hair. The volume of active formulationapplied to the hair in each application may be about 1 to about 100 mLper person depending on their length and volume of hair. In someembodiments, application of the active agent can be repeated immediately(e.g. within about 10 to 15 seconds) or between about one and fiveminutes, greater than five minutes, between about five and ten minutes,greater than ten minutes, between about ten and twenty (20) minutesafter the initial application of the active agent formulation.

The active agent formulations described herein which are applied incombination with relaxing agent(s) or immediately subsequent to theapplication of a relaxing treatment can improve hair quality, such asappearance (e.g., sheen) and feel, increase wet and dry strength, anddecrease hair breakage when the hair is subjected to subsequenttreatments, such as coloring.

In some embodiments, hair breakage can be decreased by 5, 10, 15, 20,25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75% or higher after treatmentwith the active agent, as compared to relaxed hair excluding the use ofan active agent formulation. Hair breakage is a significant problemencountered during typical hair relaxing treatments.

c. Remove the Relaxing and/or Active Agent Formulation from the Hair

The treated hair can be washed, rinsed, shampooed, or conditionedsubsequent to the relaxing process including the application of anactive agent formulation. The hair may be rinsed and subsequently washedimmediately (e.g. within 10, 15, 25, 30, 45, 60 seconds (one minute),two minutes, three minutes, four, or five minutes following application)after application of the active agent-containing formulation.Alternatively the hair may be rinsed, shampooed, or conditioned withinabout 60 minutes following application of the first and secondformulations, within about 45 minutes following application, betweenabout 5 minutes and about 20 minutes, or about 10 minutes after thefinal application of the active agent formulation to the hair, dependingon the hair type. In some embodiments of the methods described herein,the treated hair is washed, rinsed, shampooed, or conditioned about 45minutes after the application of the relaxing and active agentformulations, when they are applied simultaneously. In some embodimentsof the methods described herein, the treated hair is washed, rinsed,shampooed, or conditioned about 15 minutes after the application of anactive agent formulation, when the active formulation is appliedimmediately (i.e., within about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50,55, 60 seconds (one minute), two minutes, three minutes, four, or fiveminutes) after applying the relaxing agent formulation.

Alternately, the hair may be washed, rinsed, shampooed, or conditionedand a subsequent application of the active agent formulation may beapplied which does not have to be washed or rinsed from the hair.

The active agent(s) can covalently react with thiols present in therelaxed hair and the thiols remain crosslinked for at least one week,preferably for at least one month following application of the activeagent. The thiols may remain crosslinked for longer periods of time,such as for about three months or greater than three months, such as forat least one year following application of the active agent. Thereaction is a stable reaction, such that the thiols remain crosslinkedeven if subjected to a hair coloring treatment (simultaneous orsubsequent to the relaxing process).

EXAMPLES Example 1: Controlled Relaxing of Hair Using Bismaleate ActiveAgent in Combination with a Hydroxide-Containing Relaxer

General

Hair samples were obtained from a human subject and cut in ½ inch widewefts.

Relaxing agents: Mizani® Rhelaxer normal strength.

Active agent-containing relaxing formulation: One ounce of thecommercial hydroxide formulation was further mixed with a liquidsolution containing 0.25 ounces of a formulation having 20 weightpercent of 2,2′-(ethane-1,2-diylbis(oxy))bis(ethan-1-amine) di-maleateas the active agent.

Methods

The active agent-containing relaxation formulation was brushed into thehair sample and left for 45 minutes with periodic combing. The solutionwas subsequently washed with shampoo, conditioned, and allowed to dry.

Results

The combination of the active agent and hydroxide (lye) relaxer producedrelaxed hair that had more curl than a control (relaxing formulationwhich contains no active agent). The appearance and texture of therelaxed hair treated with a combination of the lye-based relaxing agentand active agent formulation demonstrated much improved hairconditioning (stronger, improved feel, softer with lower porosity), ascompared to the control.

Example 2: Controlled Relaxing of Hair Using Bismaleate Active Agent inCombination with a Hydroxide-Containing Relaxer

General

Hair samples were obtained from a human subject and cut in ½ inch widewefts.

Relaxing agents: Mizani® Rhelaxer normal strength.

Active agent-containing relaxing formulation: One ounce of thecommercial hydroxide formulation was further mixed with a liquidsolution containing 0.125 ounces of a formulation having 20 weightpercent of 2,2′-(ethane-1,2-diylbis(oxy))bis(ethan-1-amine) di-maleateas the active agent.

Methods

The active agent-containing relaxation formula was brushed into the hairsample and left for 45 minutes with periodic combing. The hair was thenwashed with shampoo, conditioned, and allowed to dry.

Results

As compared to the formulation tested in Example 1, the combination ofthe active agent and hydroxide (lye) relaxer but which contained areduced amount of the active agent produced relaxed hair that had lesscurl than in Example 1, but had more curl as compared to a control(relaxing agent which contains no active agent).

The appearance and texture of the relaxed hair treated with acombination of the lye-based relaxing agent and active agent formulationdemonstrated much improved hair conditioning (stronger, improved feel,softer with lower porosity), as compared to the control.

Example 3: Controlled Relaxing of Hair Using Maleic Acid as the ActiveAgent in Combination with a Hydroxide-Containing Relaxer

General

Hair samples were obtained from a human subject and cut in ½ inch widewefts.

Relaxing agents: Mizani® Rhelaxer normal strength.

Active agent-containing relaxing formulation: One ounce of thecommercial hydroxide formulation was further mixed with a liquidsolution containing 0.25 ounces of a formulation having 10 weightpercent of maleic acid as the active agent.

Methods

The active agent-containing relaxation formulation was brushed into thehair sample and left for 45 minutes with periodic combing. The solutionwas subsequently washed with shampoo, conditioned, and allowed to dry.

Results

The combination of the active agent and hydroxide (lye) relaxer resultedin relaxed hair that had more curl than a control (relaxing formulationthat contained no active agent). The appearance and texture of therelaxed hair treated with a combination of the lye-based relaxing agentand active agent formulation demonstrated much improved hairconditioning (stronger, improved feel, softer with lower porosity), ascompared to the control.

Example 4: Treating Lye Relaxed Hair Using a Bismaleate Active Agent

General

Hair samples were obtained from a human subject and cut in ½ inch widewefts.

Relaxing agents: Mizani® Rhelaxer normal strength.

Active agent formulation: A 0.5 ounce formulation of 20 weight percentof 2,2′-(ethane-1,2-diylbis(oxy))bis(ethan-1-amine) di-maleate as theactive agent was prepared in water (3 ounces).

Methods

The commercial relaxation formula was brushed into the hair sample andleft for 45 minutes with periodic combing. The hair was then washed withshampoo, conditioned, and allowed to dry.

The active agent formula was then applied to the dried, relaxed hair andallowed to stand for 15 minutes. The hair was then washed with shampoo,conditioned, and allowed to dry.

Results

The appearance and texture of hair which was first treated with alye-based relaxing agent and subsequently treated with an active agentformulation demonstrated much improved hair conditioning (stronger,improved feel, with lower porosity), as compared to the control. Afterthe treatment, some of the original curl returned to the hair ascompared to the hair immediately after lye-relaxation without the use ofan active agent.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meanings as commonly understood by one of skill in the artto which the disclosed invention belongs. Publications cited herein andthe materials for which they are cited are specifically incorporated byreference.

Those skilled in the art will recognize, or be able to ascertain usingno more than routine experimentation, many equivalents to the specificembodiments of the invention described herein. Such equivalents areintended to be encompassed by the following claims.

1-30. (canceled)
 31. A method for achieving a desired level of curl inhair as described in the description.